scholarly journals Improved Photocatalytic Water Splitting Activity of Highly Porous WO3 Photoanodes by Electrochemical H+ Intercalation

2021 ◽  
Vol 3 ◽  
Author(s):  
Ramunas Levinas ◽  
Natalia Tsyntsaru ◽  
Tomas Murauskas ◽  
Henrikas Cesiulis
Keyword(s):  
Electrochemical Impedance ◽  
Photoelectrochemical Performance ◽  
Carrier Generation ◽  
Xps Spectra ◽  
Tungsten Foil ◽  
O Vacancy ◽  
Photoexcited Charge Carrier ◽  
Subsequent Activation ◽  
Highly Porous

WO3 photoanodes are widely used in photoelectrochemical catalysis, but typically the as-synthesized material is annealed before application. It is therefore desirable to explore less energy-intensive treatments. In this study, WO3 films of up to 3.9 μm thickness were obtained by galvanostatic anodization of tungsten foil in a neutral-pH Na2SO4 and NaF electrolyte, also containing a NaH2PO2 additive (to suppress O2 accumulation on the pore walls). Additionally, the WO3 photoanodes were modified by applying a cathodic reduction (H+ intercalation) and anodic activation treatment in-situ. XPS spectra revealed that intercalation modifies WO3 films; the amount of W5+-O and O-vacancy bonds was increased. Furthermore, subsequent activation leads to a decrease of the W5+ signal, but the amount of O-vacancy bonds remains elevated. The as-prepared and reduced (intercalated & activated) films were tested as OER photoanodes in acidic 0.1 M Na2SO4 media, under illumination with a 365 nm wavelength LED. It was observed that thinner films generated larger photocurrents. The peculiarities detected by XPS for reduced films correlate well with their improved photocatalytic activity. Photo-electrochemical impedance and intensity modulated photocurrent spectroscopies were combined with steady-state measurements in order to elucidate the effects of H+ intercalation on photoelectrochemical performance. The reduction results in films with enhanced photoexcited charge carrier generation/separation, improved conductivity, and possibly even suppressed bulk recombination. Thus, the intercalation & activation adopted in this study can be reliably used to improve the overall activity of as-synthesized WO3 photoanodes, and particularly of those that are initially poorly photoactive.

scholarly journals The Electrochemical Behaviour of Quaternary Amine-Based Room-Temperature Ionic Liquid N4111(TFSI)

Catalysts ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 1315
Author(s):  
Jaanus Kruusma ◽  
Arvo Tõnisoo ◽  
Rainer Pärna ◽  
Thomas Thomberg ◽  
Mati Kook ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Room Temperature ◽  
Electrochemical Impedance ◽  
Electrochemical Behaviour ◽  
Room Temperature Ionic Liquid ◽  
Potential Range ◽  
Quaternary Amine ◽  
Xps Spectra ◽  
Strong Adsorption

In this study, we used the in situ X-ray photoelectron spectroscopy (XPS), in situ mass spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy methods, for the first time, in a detailed exploration of the electrochemical behaviour of a quaternary amine cation-based room-temperature ionic liquid, butyl-trimethyl-ammonium bis(trifluoromethylsulfonyl)imide (N4111(TFSI)), at the negatively and positively polarised molybdenum carbide-derived micro-mesoporous carbon (mmp-C(Mo2C)) electrodes that can be used as high surface area supporting material for electrocatalysts. The shapes of the C 1s, N 1s, O 1s, F 1s and S 2p XPS spectra were stable for N4111(TFSI) within a very wide potential range. The XPS data indicated the non-specific adsorption character of the cations and anions in the potential range from −2.00 V to 0.00 V. Thus, this region can be used for the detailed analysis of catalytic reaction mechanisms. We observed strong adsorption from 0.00 V to 1.80 V, and at E > 1.80 V, very strong adsorption of the N4111(TFSI) at the mmp-C(Mo2C) took place. At more negative potentials than −2.00 V, the formation of a surface layer containing both N4111+ cations and TFSI− anions was established with the formation of various gaseous compounds. Collected data indicated the electrochemical instability of the N4111+ cation at E < −2.00 V.

scholarly journals Design an Epoxy Coating with TiO2/GO/PANI Nanocomposites for Enhancing Corrosion Resistance of Q235 Carbon Steel

Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2629
Author(s):  
Shimin Chen ◽  
Bo Li ◽  
Rengui Xiao ◽  
Huanhu Luo ◽  
Siwu Yu ◽  
...  
Keyword(s):  
Carbon Steel ◽  
Photocurrent Density ◽  
Photoelectrochemical Performance ◽  
Q235 Steel ◽  
Protective Barrier ◽  
Barrier Coating ◽  
Pani Composite ◽  
Steel Protection ◽  
Q235 Carbon Steel

In this work, a ternary TiO2/Graphene oxide/Polyaniline (TiO2/GO/PANI) nanocomposite was synthesized by in situ oxidation and use as a filler on epoxy resin (TiO2/GO/PANI/EP), a bifunctional in situ protective coating has been developed and reinforced the Q235 carbon steel protection against corrosion. The structure and optical properties of the obtained composites are characterized by XRD, FTIR, and UV–vis. Compared to bare TiO2 and bare Q235, the TiO2/GO/PANI/EP coating exhibited prominent photoelectrochemical properties, such as the photocurrent density increased 0.06 A/cm2 and the corrosion potential shifted from −651 mV to −851 mV, respectively. The results show that the TiO2/GO/PANI nanocomposite has an extended light absorption range and the effective separation of electron-hole pairs improves the photoelectrochemical performance, and also provides cathodic protection to Q235 steel under dark conditions. The TiO2/GO/PANI/EP coating can isolate the Q235 steel from the external corrosive environment, and may generally be regarded a useful protective barrier coating to metallic materials. When the TiO2/GO/PANI composite is dispersed in the EP, the compactness of the coating is improved and the protective barrier effect is enhanced.

The Detection And Mapping Of Defects In Organic Coatings Using Local Electrochemical Impedance Methods

1995 ◽  
Vol 411 ◽  
Author(s):  
S. R. Taylor ◽  
M. W. Wittmann
Keyword(s):  
Electrochemical Impedance ◽  
Organic Coatings ◽  
Single Frequency ◽  
Probe Design ◽  
Coating Failure ◽  
Local Electrochemical Impedance Spectroscopy ◽  
Physical Defects ◽  
Steel Substrates ◽  
Insight Into

ABSTRACTCoating failure initiates as a local event at defects which can result from chemical heterogeneities in the resin or physical defects such as bubbles, underfilm deposits, or pinholes. The ability to detect, map the location, as well as make quantitative in-situ measurements of coating heterogeneities will help identify the source of failure (i.e. coating chemistry, method of application, cure schedule, etc.) and provide insight into the mechanisms of coating degradation. This study used a 5 electrode arrangement to perform local electrochemical impedance spectroscopy (LEIS) on coated steel substrates. Using single frequency measurements, LEIS could successfully detect and map both intentional chemical heterogeneities and physical defects such as subsurface bubbles, underfilm deposits, and pinholes. Efforts to optimize probe design and instrumentation are ongoing.

Scanning Auger and Xps Studies of Fracture Surfaces of B4C Hot Pressed with Excess Carbon

1989 ◽  
Vol 153 ◽  
Author(s):  
Benjamin M. DeKoven ◽  
Eric A. Ness ◽  
David D. Hawn
Keyword(s):  
Fracture Surface ◽  
Boron Carbide ◽  
Carbon Content ◽  
Low Dose ◽  
Xps Spectra ◽  
Excess Carbon ◽  
Fracture Surfaces ◽  
Four Point Bending ◽  
Hardness Values

AbstractA series of boron carbide materials was hot pressed with 0-7% excess carbon. The strength of each material was determined by four point bending, and found to decrease from about 600MPa to 300MPa as the carbon content increased from 0% to 7%. Diamond indentation yielded hardness values that decreased from 28.3 to 25.OGPa and toughness values that increased from 3.5 to 4.5 MPa√mover the same carbon range. Each sample was fractured in situ in ultrahigh vacuum (UHV) and examined by scanning Auger microanalysis (SAM) and XPS to determine both the elemental and chemical state distributions. For the samples with excess carbon, localized carbonrich regions are observed on fracture surfaces by SAM. XPS reveals a 50% enhancement of excess carbon on the fracture surface compared to the bulk for the sample with 7% excess carbon. A correlation was observed between surface carbon composition and the bulk toughness and hardness. The C(ls) XPS spectra were utilized to determine the nature of carbon in B4C on freshly fractured and Ne+ bombarded surfaces. Two distinct peaks were observed in the C(ls) region. Low dose ion bombardment resulted in a single broad C(ls) peak at the midpoint of the two initial peaks. It can be inferred from this data that there are C-C-C intericosahedral linkages in B4C.

Mechanistic Insights into the Spontaneous Reaction Between CO2 and La2-xSrxCuO4

2021 ◽  
Author(s):  
Alexander William Henry Whittingham ◽  
Jordan Lau ◽  
Rodney David Lucien Smith
Keyword(s):  
Electrochemical Impedance ◽  
Co2 Reduction ◽  
Active Surface ◽  
Structural Instability ◽  
Redox Couple ◽  
Surface Sites ◽  
Carbonate Ions ◽  
Redox Active ◽  
Spontaneous Reaction

Layered perovskites such as La2-xSrxCuO4 are active electrocatalysts for CO2 reduction, but they suffer from structural instability under catalytic conditions. This structural instability is found to arise from the reaction of CO2 with surface sites. Variable scan rate voltammetry shows the growth of a Cu-based redox couple when potentials cathodic of 0.6 V vs. RHE are applied in the presence of CO2. Electrochemical impedance spectroscopy identifies a redox active surface state at this voltage, whose concentration is increased by electrochemical reduction in the presence of CO2. In-situ spectroelectrochemical FTIR identifies surface bound carbonates as being involved formation of these surface sites. The orthorhombic lattice for La2-xSrxCuO4 is found to uniquely enable monodentate binding of (bi)carbonate ions from solution as well as bidentate carbonate ions through reaction with CO2. The incorporation of Sr(II) induces a transition to a tetragonal lattice, for which only monodentate carbonate ions are observed. It is proposed that the binding of carbonate ions in a bidentate fashion generates sufficient strain at the surface to result in amorphization at the surface, yielding the observed Cu(II)/Cu(I) redox couple.

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